Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/12—Powders or granules
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

• the present invention relates to new agrochemical compositions, in particular tablets, and their method of manufacture.
• the present invention relates more particularly to solid, non-dusty forms which may contain active ingredients which are non-crystalline at room temperature and in particular naturally liquid, crystalline or non-crystalline solubilized in a non-aqueous solvent and in particular of pasty synthesis, or which may contain active ingredients sensitive to hydrolysis or thermosensitive.
• JP-A-04 273802 describes compositions of an agrochemical active principle in the form of an adsorbed liquid, comprising a soluble filler, an effervescent couple, a disintegrant and optionally a hydrophilic super-disintegrant.
• US-A-5 830 576 describes compositions of a liquid agrochemical active ingredient, comprising urea, and optionally a hydrophilic super disintegrant and a binder.
• EP-A-0 480 679 describes compositions of an agrochemical active principle liquid or dissolved in a solvent, comprising silica, an effervescent couple, a hydrophilic super-disintegrant, a soluble filler, and a binder.
• the cost of agrochemicals is an essential aspect which distinguishes it from pharmaceutical products.
• the quantities used in agriculture are significant taking into account the surfaces to be treated, which necessitates minimizing the cost of the formulation.
• Active ingredients are already known formulated in the form of powders but which have the disadvantage of emitting dust, which poses a risk of inhalation of the product by its user when the latter pours it into a sprayer.
• these methods make it difficult to work on non-crystalline active ingredients at room temperature such as liquid or pasty active ingredients.
• Some solid active ingredients are more effective in dissolved form. This is the reason why these are preferably formulated as an Emulsifiable Concentrate (EC) or an emulsion (EW). Techniques are still being sought to formulate such active ingredients in a non-dusty solid form.
• EC Emulsifiable Concentrate
• EW emulsion
• the present application relates to a new solid formulation, in particular pre-dosed, in tablets, characterized in that it comprises by weight - 0.1 to 60% of a non-crystalline agrochemical active principle at room temperature ( pasty, solubilized or liquid, preferably the latter two), or optionally of a crystalline agrochemical active ingredient in oily suspension, - 1 to 30% of an effervescent couple, - 1 to 30% of an adsorbent support - 0, 01 to 10% of a hydrophilic super disintegrant, - 5 to 60% of a water-soluble or hydrophilic filler for direct compression, - 0.5 to 10% of a binder, and optionally - 1 to 30% of a filler insoluble - 0.5 to 30% of an insoluble filler for direct compression, - 0.5 to 10% of a couple of surfactants, one wetting, the other dispersing.
• a non-crystalline agrochemical active principle at room temperature pasty, solubilized or liquid, preferably the latter two
• the non-crystalline agrochemical active principle at room temperature is pasty or preferably liquid or dissolved in a non-aqueous solvent and in particular a synthetic solvent.
• the active principle will in particular be an active principle dissolved in a non-aqueous solvent. It is possible to dissolve in a non-aqueous solvent both a crystalline or amorphous solid active principle as well as a pasty or liquid active principle.
• the solvent is for example a mineral oil or a vegetable oil such as rapeseed oil. Mention may be made, for example, as an agrochemical active principle which is not crystalline at room temperature, an insecticide, a herbicide, a fungicide or a pheromone.
• the liquid or pasty insecticidal active ingredient may for example be an organophosphorus compound such as pirimiphos-methyl, malathion, a carbamate such as carbosulfan, a natural or synthetic pyrethroid such as bioresmethrin, bioallethrin, cypermethrin or bifenthrin.
• the active ingredient insecticide solubilized can be for example a natural or synthetic pyrethroid like deltamethrin or lambda-cyalothrin, an organo-halogenated like endosulfan, or a chloronicotinile like imidacloprid or acetamiprid.
• the insecticidal active principle can be in particular pyrethrum or a natural or synthetic pyrethroid like deltamethrin or cypermethrin and particularly the latter.
• the insecticide active ingredient can also be a combination of active ingredients, prepared or not prepared in advance.
• active ingredient insecticide also refers to related active ingredients such as nematicides or acaricides.
• triazolinones such as carfentrazone-ethyl, aryloxyphenoxy-propionates (fops) such as fluazifop-p-butyl, chloroacetamides such as acetochlor, s-metolachlor or thiocarbamates such as prosulfocarb.
• solubilized herbicide there may be mentioned for example aryloxyphenoxy-propionates (fops) such as cyhalofop-butyl, clodinafop-propargyl, or diclofop, or cyclohexane-dione oxime such as clethodime or hydroxybenzonitriles such as bromoxynile or l 'ioxynil.
• fops aryloxyphenoxy-propionates
• fops cyclohexane-dione oxime
• clethodime clethodime
• hydroxybenzonitriles such as bromoxynile or l 'ioxynil.
• herbicidal active ingredient also refers to related active ingredients such as growth regulators.
• the liquid or pasty fungicide can be for example various heterocycles in particular triazoles like propiconazole or tetaconacon, azoles like technical prochloraz, morpholines like fenpropimorph, phenylamides like methalaxyl-M or dinitrophenol derivatives like dinocap .
• the solubilized fungicide can be, for example, diverse heterocycles, in particular azoles such as tebuconazole, cyproconazole or diniconazole, or an oximinoacetate such as trifloxystrobin.
• Liquid or pasty pheromones can be, for example, dispalure, dodec-8-enyl acetate, ethyl 4-methyloctanoate, gossyplide methyl eugenol or z) -hexadec-11-enyl acetate. It is obviously possible to use a single active principle or a combination of active principles as we have seen.
• the active ingredient as used at the start can be liquid or pasty. In these cases, it can be used respectively directly or in dissolved form, in particular in the form of an emulsifiable concentrate.
• the active ingredient used at the start can also be solid (amorphous or crystalline).
• the non-crystalline agrochemical active principle at room temperature is pasty or of preferably solubilized in a non-aqueous solvent and in particular a synthetic solvent.
• the active principle is advantageously used in the form of an emulsifiable concentrate comprising more than 30% and preferably more than 50% of active principle and one or more surfactants.
• the solvent used is advantageously an organic solvent or a mixture of organic solvents.
• a liquid or pasty active principle can also be used without prior solubilization.
• the implementation will preferably be hot, for example at a temperature of 40 to 80 ° C for the pasty active ingredients.
• the active ingredient can represent from 0.1 (for very low dose active ingredients such as sulfonylureas) to 60% of the solid formulation, in particular from 1 to 60%, preferably from 1% to 50%, especially from 1% to 40%.
• the above solid formulation also contains a solvent for the active principle forming an emulsion with water and at least one surfactant.
• the solvent may for example be an aromatic petroleum solvent, for example Cg or C-10 such as those sold under the brand Solvesso®.
• the effervescent couple can represent from 1 to 30% of the solid formulation, preferably from 2% to 20%, in particular from 2% to 10%, very particularly from 3% to 8%.
• An effervescent couple conventionally comprises an acid which is preferably a water-soluble or water-soluble organic acid such as fumaric acid or citric acid and a carbonated base, in particular an alkali carbonate or hydrogen carbonate such as sodium hydrogen carbonate.
• Each of the elements of the pair can represent from 1 to 20% of the solid formulation, preferably from 2% to 20%, in particular from 5% to 15%, very particularly from 4% to 8%.
• the adsorbent support can be for example a cellulose derivative, starches, silicas or silicates, preferably a silica and particularly a fumed or precipitated silica with high adsorbent power, possibly colloidal, for example of the Aérosil® type.
• Aeroperle® or Sipemat® or an amorphous silica gel.
• the adsorbent support can represent from 1 to 30% of the solid formulation, preferably from 5% to 20%, in particular from 8% to 15%.
• the main function of the adsorbent support is to allow the transformation of the active principle into a pulverulent mass. This is why high doses of active ingredient will correspond to high doses of adsorbent support.
• the hydrophilic super-disintegrant is preferably a disintegrant, weakly binding and very swelling, for example of the crosslinked carmellose type (crosslinked carboxymethyl cellulose), preferably crosslinked povydone (polyvinyl pyrrolidone - hereinafter crosslinked PVP) or crosslinked carboxymethyl starch or conventional disintegrants of native corn starch type.
• crosslinked carmellose type crosslinked carboxymethyl cellulose
• povydone polyvinyl pyrrolidone - hereinafter crosslinked PVP
• crosslinked carboxymethyl starch or conventional disintegrants of native corn starch type.
• hydrophilic super disintegrant of pregelatinized corn starches, crosslinked polyacrylates such as that sold by the company ROHM and HAAS under the name Acusol.772 @, amorphous celluloses and microcrystalline celluloses.
• the hydrophilic super disintegrant can represent from 0.01 to 10% of the solid formulation, in particular from 0.5% to 10%, preferably from 1% to 5%, particularly from 2% to 4%, very particularly from 2% less than 3%.
• the water-soluble or hydrophilic filler for direct compression may for example be a derivative or mixture of derivatives of starches, sugars or polyols, preferably a compound of the polyol, sorbitol, mannitol, maltodextrin, lactose or pregelatinized starch type. Mention may be made, for example, of the product marketed by the company ROQUETTE under the names
• Pearlitol®, Neosorb® or Starlac® which is a compound excipient, comprising lactose and starch. Mention may also be made, as water-soluble or hydrophilic filler for direct compression, of sodium tripolyphosphate.
• the soluble filler for direct compression can represent from 5 to 60% of the solid formulation, preferably from 10% to 50%, in particular from 20% to 40%.
• the binder can be, for example, a starch, sugar, polyol, cellulosic, vinyl or acrylic derivative, preferably a binder of adhesive power which can be chosen from a range of adhesive power, for example a binder of the carmellose or povydone type. linear.
• binder sold by the company BASF under the name Luvitec®K30.
• binder mention may also be made of polyethylene glycol, sodium toluene sulfonate and hydrolyzed corn starches, for example that sold by the company ROQUETTE under the name Lycatab DSH®.
• the binder can represent from 0.5 to 10% of the solid formulation, preferably from 0.5 to 9.5%, particularly from 1% to 8%, very particularly from 2% to 6%.
• the above solid formulation contains a lubricant. This can represent from 0.1 to 2% of the solid formulation pre-dosed in tablets, preferably from 0.2% to 1%, very particularly from 0.4% to 0.6%.
• the lubricant can be hydrophilic of the sucroester type (DUB) or lipophilic such as magnesium or sodium stearate.
• DAB sucroester type
• lipophilic such as magnesium or sodium stearate.
• the applicant has realized that when using certain compositions, the formation of aggregates is observed which tends to clog the filters of the sprayers.
• the addition of an insoluble filler solves this problem. This is why, in other preferential conditions for implementing the invention, the above solid formulation contains an insoluble filler. This can represent from 1 to 30% of the solid formulation pre-dosed in tablets, preferably from 5% to 25%, in particular from 15% to 20%.
• This insoluble filler is an adsorbent of the active principle and thus is used at the same time as the adsorbent support.
• the insoluble filler may for example be a derivative of calcium salts, microcrystalline celluloses of varying densities and particle sizes as well as the compound excipients resulting therefrom very particularly of the type Avicel® or Microcel®.
• kaolins such as Argirec® B24F clay, diatoms, bentonites and silicates (including aluminosilicates) are also classified in this category of excipients.
• the above solid formulation contains an insoluble filler for direct compression. This can represent up to 30% of the solid formulation pre-dosed in tablets, preferably from 5% to 20%, in particular from 10% to 17%.
• the insoluble filler for direct compression can for example be a derivative of calcium salts, celluloses or starches, preferably a compound facilitating disintegration by wicking effect and particularly microcrystalline celluloses of varying densities and particle sizes as well as the excipients composed of resulting in particular from the Avicel® or Microcel® type.
• kaolins and silicates are classified in this category of excipients.
• the above solid formulation contains a pair of surfactants, one wetting, the other dispersant.
• the surfactants can for example be chosen from cellulose derivatives such as lignosulfonates, synthetic polymers such as polycarboxylates such as that marketed by the company HUNTSMAN under the name Tersperse 2700®, sodium sulfonate, ethoxylated alcohols, dodecylbenzene sulfonate, sulfosuccinates, alpha olefin sulfonates such as that sold by the company HUNTSMAN under the name Terwet 1004®.
• cellulose derivatives such as lignosulfonates
• synthetic polymers such as polycarboxylates such as that marketed by the company HUNTSMAN under the name Tersperse 2700®
• sodium sulfonate sodium sulfonate
• ethoxylated alcohols ethoxylated alcohols
• dodecylbenzene sulfonate sulfosuccinates
• adjuvants usually used in these compositions such as various wetting agents, dispersants, emulsifiers, or preservatives as well as disintegration aids such as - sodium salts such as sodium sulfate.
• the adjuvants are preferably present in said emulsifiable concentrate.
• agrochemical tablet compositions of the present invention can be prepared according to methods known per se and in particular by direct compression.
• the present invention therefore also relates to a process for the preparation of a composition described above, characterized in that the active ingredient (s) is mixed in liquid form, if necessary after dissolving, to allow their adsorption, with the various excipients, and then the compression is carried out, preferably direct, of the mixture.
• the active ingredient (s) is mixed, optionally after dissolving, with the adsorbent support and optionally the insoluble filler to obtain an adsorbent support impregnated with active ingredient, then with the other excipients, and then the compression of the mixture.
• the adsorption of the active ingredient (s) begins on the adsorbent support.
• an insoluble filler used as an adsorbent of the active principle it is preferably used at the same time as the adsorbent support.
• a pair of surfactants it is preferably used after, in particular just after the adsorbent support. The whole is advantageously ground after adsorption and if appropriate after the addition of the insoluble filler used as adsorbent and
• direct compression of the mixture is meant a direct compression of a mixture of powders, including optionally the active principle (s) impregnated, without prior granulation.
• granulation is carried out, preferably without wetting with water, before compression. This can be done by compacting-grinding or by dry granulation in a mixer, preferably of the pedestal type, for example L ⁇ dige.
• the compression is carried out using a rotary machine in particular with forced feeding and particularly with pre compression.
• the active principle When a particular effect is to be obtained, for example a shock effect for an insecticide, whatever its physical form, the active principle will be dissolved beforehand in a solvent, optionally with the aid of surfactant (s) ( s), to produce an emulsifiable concentrate which will be used as a liquid active principle.
• the solvent used may for example be an aromatic petroleum solvent, for example Cg or C10, such as those sold under the brand Solvesso®.
• the agrochemical compositions, in particular pre-dosed in tablets which are the subject of the present invention have very advantageous properties and qualities.
• These properties are illustrated below in the experimental part. They justify the use of the agrochemical compositions described above, in agriculture or gardening. This is why the invention also relates to the use of the above agrochemical compositions in the treatment of pests or pests of vegetation or the control of vegetation, in particular undesirable.
• the above agrochemical composition can be sprayed after dilution in a sufficient amount of water.
• the subject of the invention is as much the provision of new agrochemical compositions as other compositions than those which may have been described in the prior art. Those described in the literature are therefore excluded.
• the preferential conditions for using the agrochemical compositions described above also apply to the other objects of the invention referred to above, in particular to the methods for preparing them.
• the preparation is carried out by simple mixing with stirring. Cypermethrin, which is in the form of a resin, is used hot (pre-heating> 54 ° C).
• An emulsifiable concentrate of tebuconazole was produced having the following composition by weight:
• Tebuconazole which is in crystalline form, is dissolved hot (between 30 and 40 ° C).
• Cypermethrin which is in the form of a resin, is used hot at 54 ° C.
• An impregnated silica is obtained which is used as it is in stage B.
• Stage B A mixture for compression equivalent to 100 tablets of 2 g is prepared with Turbula® in the following proportions:
• Stage C The Stage B compression mixture was compressed on a single-punch Frogerais alternative compression device. , A 20 mm punch was used. 2 g tablets containing 10% technical cypermethrin with good cohesion were obtained.
• Stage A Sipernat® 50 S precipitated silica is installed in a base mixer and then the cypermethrin solution of Preparation 1 is gradually added through a nozzle in the following proportions:
• stage B An impregnated silica is used, used as it is in stage B.
• Stage B A mixture for compression equivalent to 100 tablets of 2 g is prepared with Turbula® in the following proportions:
• stage A The 70% cypermethrin solution and Sipernat® 50 S come from stage A).
• Stage C The compression mixture from stage B was compressed on an alternative Frogerais type single-punching device. . A 20 mm punch was used. 2 g tablets containing 21.6% cypermethrin 70% having good cohesion were obtained.
• Example 4 Cypermethrin Tablets Stage A: 191 g of Sipernat® 50 S precipitated silica and 1146 g of Argirec B24F clay are installed in a base mixer. Homogenize the mixture then 583 g of cypermethrin solution from Preparation 1 are gradually added through a nozzle. An impregnated mixture (silica + clay) is obtained, used as it is in stage B. Stage B: The mixture obtained in stage A remains in the base mixer: a couple of dispersing / wetting surfactants are added to it in the following proportions:
• Stage C The mixture of stage B is ground in an Alpine® hammer mill.
• Stage D A mixture for compression equivalent to 100 tablets of 2 g is prepared with Turbula® in the following proportions:
• Stage E The stage D compression mixture was compressed on a single-punch Frogerais alternative compression device. A 20 mm punch was used. 2 g tablets containing 15.25% cypermethrin 70% having good cohesion were obtained.
• Stage C 78 g of the granules prepared in stage B are mixed with:
• Stage D The compression mixture of stage C was compressed on an alternative compression device of the one-punch Frogerais type. A 20 mm punch was used. 2.2 g tablets 23.7% cypermethrin 70% were obtained. •. EXAMPLE 6 Cypermethrin Tablets with Granulation and Use of Water
• Stage A Granulation is carried out by mixing the silica, PVP K 30 and Kollidon® for 5 to 10 minutes in a base mixer, and gradually adding the cypermethrin solution from Preparation 1 through a nozzle as well. as water through a nozzle, in the following proportions:
• the granules obtained are dried in a fluidized air bed in order to obtain a residual water content of less than 2%. Granules are obtained less oily than in Example 3. Stage B: After granulation, the granule is calibrated on an Erweka type ribbon calibrator
• Stage C 78 g of the granules prepared in stage B are mixed
• Stage D The compression mixture from stage C was compressed on an alternative Frogerais type single-punching device. A 20 mm punch was used. 3 g tablets containing 23.1% cypermethrin 70% were obtained.
• the tablets of Examples 1 to 6 have a suspensibility measured according to the Cipac MT 161 test greater than 60%.
• Stage A Sipernat® 50 S precipitated silica is installed in a base mixer then a solution of deltamethrin from Preparation 2 is gradually added through a nozzle in the following proportions:
• Stage B A mixture for compression equivalent to 100 tablets of 2 g is prepared with Turbula® in the following proportions:
• Stage C The Stage B compression mixture was compressed on a single-punch Frogerais alternative compression device. A 20 mm punch was used. 2 g tablets containing 15.25% deltamethrin 30% with good cohesion were obtained.
• Stage A Sipernat® 50 S precipitated silica is installed in a base mixer then a solution of tebuconazole of Preparation 3 is gradually added through a nozzle in the following proportions:
• Stage B A mixture for compression equivalent to 100 tablets of 2 g is prepared with Turbula® in the following proportions:
• Stage C The Stage B compression mixture was compressed on a single-punch Frogerais alternative compression device. A 20 mm punch was used. 2 g tablets containing 15.25% tebuconazole 30% having good cohesion were obtained.

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• Dentistry (AREA)
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• Engineering & Computer Science (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Wood Science & Technology (AREA)
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• Agricultural Chemicals And Associated Chemicals (AREA)

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  • 2003-11-19 FR FR0313556A patent/FR2862187B1/fr not_active Expired - Lifetime
• 2004
  • 2004-11-18 EP EP04805477A patent/EP1684584A1/de not_active Withdrawn
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